Supramolecular encrypted fluorescent security ink compositions

ABSTRACT

Fluorescent dyes, ink compositions comprising the dyes, methods and devices for printing the ink compositions, images printed using the ink compositions and methods for authenticating the printed images are provided. The fluorescent dyes are heterorotaxanes that include large macrocyclic rings around fluorophores and are capable of emitting solid-state fluorescence. When the heterorotaxanes are combined with encapsulating agents and competitive binding agents in aqueous solution, the resulting ink composition exhibits a complex, dynamic equilibrium that provides a tunable fluorescence emission spectrum with a non-linear response to the dye concentration.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Provisional PatentApplication No. 62/057,102 that was filed Sep. 29, 2014, the entirecontents of which are hereby incorporated by reference.

BACKGROUND

The global economic and social impacts of counterfeiting result in theloss of 600 billion US Dollars annually (1). The practice infringes onintellectual property and impinges detrimentally on society, especiallyin the arenas of health (2), commerce, and finance (3). A variety ofsecurity technologies (4) have already been developed using innovativesecurity printing materials (5) as crucial anti-counterfeiting measuresto deter counterfeiters. Although fluorescent dyes, which can be appliedeasily to different surfaces inexpensively, have been implemented widelyto protect high-value merchandise, government documents, and banknotes,these dyes are familiar to counterfeiters. In response, next-generationfluorescent dyes with properties such as multi-color emission (6, 7),luminescence up-conversion (8), fluorescent lifetime encoding anddecoding (9), and stimulus-responsive color-tuning (10, 11) have allbeen suggested as ways to counteract forgery.

Important considerations, when designing fluorescent security dyes,include (i) tunable emission wavelengths, (ii) stimulus-responsiveproperties, (iii) susceptibility to mimicry, as well as accessibility,compatibility with current printing technologies and cost. Solid-statefluorescent dyes with tunable (9, 12) and stimulus-responsive (13-15)emission wavelengths remain challenging to design. Most of the currentdyes, which exhibit stimulus-induced spectroscopic changes, arecrystalline with slow response times and narrow tunable wavelengthwindows.

SUMMARY

Ink compositions comprising fluorescent dyes, methods and printheads forprinting the ink compositions, images printed using the ink compositionsand methods of authenticating the printed images are provided.

One embodiment of an ink composition comprising a fluorescent dyecomprises: (a) water; and (b) a heterorotaxane. The heterorotaxanecomprises: (i) a substantially linear molecule comprising a centralfluorophoric group, a first fluorophoric end group on one end of thesubstantially linear molecule, and a second fluorophoric end group onthe opposite end of the substantially linear molecule; (ii) a firstmacrocyclic ring encircling the central fluorophoric group; (iii) asecond macrocyclic ring encircling a portion of the substantially linearmolecule between the first fluorophoric end group and the centralfluorophoric group; and (iv) a third macrocyclic ring encircling aportion of the substantially linear molecule between the secondfluorophoric end group and the central fluorophoric group. The inkcomposition also, optionally, includes: (c) an encapsulating agentcomprising a macrocyclic ring that is capable of encapsulating one orboth of the first and second fluorophoric end groups; and (d) acompetitive binding agent that competes with one or both of the firstand second fluorophoric end groups for binding the encapsulating agent.

One embodiment of a printhead comprises: a plurality of different inkchannels, the different ink channels containing fluorescent inkcompositions that comprise: (a) water; and (b) a heterorotaxane. Theheterorotaxane comprises: (i) a substantially linear molecule comprisinga central fluorophoric group, a first fluorophoric end group on one endof the substantially linear molecule, and a second fluorophoric endgroup on the opposite end of the substantially linear molecule; (ii) afirst macrocyclic ring encircling the central fluorophoric group; (iii)a second macrocyclic ring encircling a portion of the substantiallylinear molecule between the first fluorophoric end group and the centralfluorophoric group; and (iv) a third macrocyclic ring encircling aportion of the substantially linear molecule between the secondfluorophoric end group and the central fluorophoric group. The inkcomposition also, optionally, includes: (c) an encapsulating agentcomprising a macrocyclic ring that is capable of encapsulating one orboth of the first and second fluorophoric end groups; and (d) acompetitive binding agent that competes with one or both of the firstand second fluorophoric end groups for binding the encapsulating agent.By filling different ink channels with different formulations of thefluorescent ink compositions, the printhead can be configured to printpolychromic images.

One embodiment of a method for printing an image on a substratecomprises applying one or more fluorescent ink compositions onto asurface of the substrate and allowing the one or more appliedfluorescent ink composition to dry, wherein the fluorescent inkcompositions comprise: (a) water; and (b) a heterorotaxane. Theheterorotaxane comprises: (i) a substantially linear molecule comprisinga central fluorophoric group, a first fluorophoric end group on one endof the substantially linear molecule, and a second fluorophoric endgroup on the opposite end of the substantially linear molecule; (ii) afirst macrocyclic ring encircling the central fluorophoric group; (iii)a second macrocyclic ring encircling a portion of the substantiallylinear molecule between the first fluorophoric end group and the centralfluorophoric group; and (iv) a third macrocyclic ring encircling aportion of the substantially linear molecule between the secondfluorophoric end group and the central fluorophoric group. The inkcomposition also, optionally, includes: (c) an encapsulating agentcomprising a macrocyclic ring that is capable of encapsulating one orboth of the first and second fluorophoric end groups; and (d) acompetitive binding agent that competes with one or both of the firstand second fluorophoric end groups for binding the encapsulating agent.Polychromic images can be printed by applying different formulations ofthe fluorescent ink compositions onto the surface of the substrate.

One embodiment of a printed substrate comprises: a substrate; and one ormore fluorescent inks that form an image on the surface of thesubstrate, the fluorescent inks comprising: a heterorotaxane comprising:(i) a substantially linear molecule comprising a central fluorophoricgroup, a first fluorophoric end group on one end of the substantiallylinear molecule, and a second fluorophoric end group on the opposite endof the substantially linear molecule; (ii) a first macrocyclic ringencircling the central fluorophoric group; (iii) a second macrocyclicring encircling a portion of the substantially linear molecule betweenthe first fluorophoric end group and the central fluorophoric group; and(iv) a third macrocyclic ring encircling a portion of the substantiallylinear molecule between the second fluorophoric end group and thecentral fluorophoric group. The ink also, optionally, includes anencapsulating agent comprising a macrocyclic ring that is capable ofencapsulating one or both of the first and second fluorophoric endgroups; and a competitive binding agent that competes with one or bothof the first and second fluorophoric end groups for binding theencapsulating agent. Some embodiments of the printed substrates comprisepolychromic images comprising a plurality of different fluorescent inks.

The polychromic images can be authenticated by: applying anauthentication reagent over the polychromic image, wherein theauthentication reagent induces a change in the fluorescence emissionspectrum of the polychromic image; and comparing the change in thefluorescence emission spectrum of the polychromic image against a knownfluorescence emission spectrum change for an authentic printedsubstrate.

Other principal features and advantages of the invention will becomeapparent to those skilled in the art upon review of the followingdrawings, the detailed description, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Illustrative embodiments of the invention will hereafter be describedwith reference to the accompanying drawings.

FIGS. 1A-F. Synthesis and photo-physical properties of theheterorotaxane. FIG. 1A. Synthesis of the heterorotaxane R4.4Cl from thestopper 1.Cl, the dumbbell precursor 2.2Cl, CB6 and γ-CD. FIG. 1B.Graphical representation of the aggregation of R⁴⁺ monomers in responseto changes in concentration or temperature. FIG. 1C. UV/Vis absorption(solid lines) and normalized fluorescence spectra (excitation: dashedlines, emission: dotted lines) of aqueous solutions of R4.4Cl, stopper1.Cl and dumbbell precursor 2.2Cl. FIG. 1D. Concentration dependent(25-500 μM) UV/Vis absorption spectra of R4.4Cl at 25° C. in water. FIG.1E. Normalized concentration dependent (25-500 μM) fluorescence emissionspectra (λ_(excitation)=341 nm) of R4.4Cl at 25° C. in water. FIG. 1F.Temperature dependent (2-80° C.) induced circular dichroism (ICD)spectra (200 μM) of R4.4Cl in water.

FIGS. 2A-C. Equilibrium network and solid-state fluorescence studies.FIG. 2A. Graphical representation of the equilibria involving R⁴⁺ in thepresence of γ-CD and CAs. FIG. 2B. Solid-state fluorescence spectra(λ_(excitation)=347 nm) of R4.4Cl upon adding 0-200 equiv of γ-CD,followed by 200 equiv of Ad.Cl. FIG. 2C. Powders obtained fromhomogeneous mixtures of R4.4Cl and varying amounts (0-200 equiv) of γ-CDand Ad.Cl (200 equiv) under UV light.

FIGS. 3A-M. Supramolecular encryption with fluorescent security inks.FIG. 3A. R4⊂γ-CD₂ ink written on different paper media (newsprint,coated and uncoated rag paper, banknotes, copy, matte, and glossy whitepaper) under UV light. FIG. 3B. A QR code printed using a customizedblack inkjet cartridge filled with R⁴⁺⊂γ-CD₂ under UV light.

FIG. 3C. Graphical representations of a customized tri-color inkjetcartridge, in which aqueous solutions of R4.4Cl/γ-CD (R4.4Cl: 1 mM,γ-CD: 200 mM), a CA and γ-CD occupy the yellow, magenta, and cyan colorchannels, respectively. FIG. 3D. Fluorescent replica of van Gogh's‘Sunflowers’ on rag paper printed using the customized tri-color inkjetcartridge under UV and natural light. FIG. 3E. Digital replica of FIG.3D. FIG. 3F. A standard color palette. FIG. 3G. Color palette imageproduced using the customized tri-color inkjet cartridge with Ad.Cl (200mM) in the CA channel. FIG. 3H. Color palette image produced using thecustomized tri-color inkjet cartridge with AdMe.Cl (200 mM) in the CAchannel. FIG. 3I. Color palette image produced using the customizedtri-color inkjet cartridge with AdMe.Cl (20 mM) in the CA channel. FIG.3J. Color palette image produced using the customized tri-color inkjetcartridge with γ-CD (20 mM) in the γ-CD channel. FIG. 3K. Color paletteimage produced using the customized tri-color inkjet cartridge with γ-CD(100 mM) with PyMe.Cl (4 mM), in the γ-CD channel. FIG. 3L. Fluorescentreplica of Briex's ‘Apostelhoeve Wine Estate Maastricht’ printed usingan inkjet cartridge with the same setting as FIG. 3K under UV andnatural light. FIG. 3M. Digital replica of FIG. 3L.

FIGS. 4A-C. Fraud protection and detection using the security ink. FIG.4A. Polychromic color palettes produced by the customized inkjetcartridge (center) and its derivatives (around the periphery, afterprinting a layer of authentication reagents) under UV light. FIG. 4B. Ademonstration of fluorescent colors produced by R4-based inks withdifferent formulations that appear almost identical (cf. 1b and 1c, or2b and 2c), but are distinguished (cf. 1a and 1d, or 2a and 2d) using anauthentication agent. No distinguishable color change is observed (line3) using rhodamine B (RhB). FIG. 4C. A flowchart for the supramolecularencryption and chemical authentication processes.

FIGS. 5A and B. RGB printing inkjet printer cartridges setup. FIG. 5A.tri-color inkjet cartridge loaded with R4.4Cl/γ-CD (2 mL, R4.4Cl: 0.25mM, γ-CD: 10 mM), AdMe.Cl (2 mL, 50 mM), and PyMe.Cl/γ-CD (2 mL,PyMe.Cl: 1 mM, γ-CD: 25 mM), in three channels respectively. FIG. 5B. Acombination use of black inkjet cartridge loaded with the aqueoussolution of PyMe.Cl (1 mM) and tri-color inkjet cartridge withR4.4Cl/γ-CD (2 mL, R4.4Cl: 0.25 mM, γ-CD: 10 mM), AdMe.Cl (2 mL, 50 mM),and γ-CD (2 mL, γ-CD: 25 mM), in three channels respectively.

DETAILED DESCRIPTION

Fluorescent dyes, ink compositions comprising the dyes, methods andprintheads for printing the ink compositions, images printed using theink compositions and methods for authenticating the printed images areprovided.

The fluorescent dyes are heterorotaxanes that include large macrocyclicrings around fluorophores and are capable of emitting solid-statefluorescence. When the heterorotaxanes are combined with encapsulatingagents and competitive binding agents in aqueous solution, the resultingink composition exhibits a complex, dynamic equilibrium that provides atunable fluorescence emission spectrum with a non-linear response to thedye concentration. As a result, the ink compositions are useful assecurity inks for printing polychromatic encrypted images that aredifficult to reproduce, but relatively easy to authenticate.

The heterorotaxanes are compounds comprising a substantially linearmolecule (sometimes referred to as a rod) and one or more macrocyclicrings encircling the substantially linear molecule, such that they arebound together in a threaded supramolecular structure by non-covalentforces. The substantially linear molecule comprises at least one centralfluorophoric group along its length and a bulky fluorophoric end groupat each end that prevent the dethreading of the macrocyclic rings. (Thebulky end groups on heterorotaxanes are sometimes referred to asstoppers.) In the fluorescent dyes, the central fluorophoric group isencircled by one of the macrocyclic rings.

One embodiment of a fluorescent dye, denoted “R4.4Cl” is shown in FIG.1A. This dye comprises a substantially linear molecule comprising acentral fluorophoric group, a first fluorophoric end group on one end ofthe substantially linear molecule, and a second fluorophoric end groupon the opposite end of the substantially linear molecule. A firstmacrocyclic ring encircles the central fluorophoric group. A secondmacrocyclic ring encircles a portion of the substantially linearmolecule between the first fluorophoric end group and the centralfluorophoric group and a third macrocyclic ring encircles a portion ofthe substantially linear molecule between the second fluorophoric endgroup and the central fluorophoric group.

Examples of fluorescent dyes include those that comprises twoN-(1-pyrenylmethyl)ethylammonium units and one2,9-diethyl-2,9-diazaperopyrenium unit connected by two 1,2,3-triazoleunits, penetrating a cucurbit[6]uril ring, a γ-cyclodextrin, and anothercucurbit[6]uril ring in sequence. Therefore, these dyes can becharacterized by formula I:

where X, Y and Z are fluorophoric groups; N⁺ is a quarternary nitrogencation; n has a value of 6, 7 or 8; R₁, R₂, R₃ and R₄ are selectedindependently from the group consisting of H, alkyl groups, alkenylgroups, alkynyl groups, aryl groups, OH, NH₂, SH, F, Cl, Br, I, PR′₂,CHO, COOR′, COOM, CH₂OR′, CH₂OM, OR′, NHCOR′, CONHR′, CONHM, CONR′₂, N₃,NO₂, B(OR′)₂, B(OM)₂, CN, NR′³⁺, PR′³⁺, POR′₂, and OM, where R′ isselected independently from the group consisting of H, alkyl groups,alkenyl groups, alkynyl groups, and aryl groups and M is selectedindependently from the group consisting of Li, Na, K, Rb, and Cs; and C⁻is an organic or inorganic negatively charged ion.

The fluorophoric groups may comprise organic heterocyclic groups and/ororganic aromatic groups. Specific examples of fluorophoric groups thatcan be incorporated into the substantially linear chain, include but arenot limited to pyrene, 2,9-diethyl-2,9-diazaperopyrenium dication,anthracene, coumarin, acridine, 9-aminoacridine, fluorescein,naphthofluorescein, resofurin, rhodamine B, rhodamine 6G, perylenediimide, naphthalene diimide, propidium, boron difluoridedipyrromethene, phthalocyanine, cyanine, porphyrin, and theirderivatives. In some embodiments, N⁺ is selected from the groupconsisting of ammonium, methyl ammonium, dimethyl ammonium andpyridinium cations. In some embodiments, C⁻ is selected from the groupconsisting of F⁻, Cl⁻, Br⁻, I⁻, PF₆ ⁻, BF₄ ⁻, CF₃COO⁻, CH₃COO⁻, SO₄ ²⁻,SO₃ ²⁻, NO₃ ⁻, NO₂ ⁻, CO₃ ²⁻, HCO₃ ⁻, ClO₄ ⁻, PO₄ ³⁻, HPO₄ ²⁻, H₂PO₄ ⁻,CN⁻, and SCN⁻.

In one embodiment of dye having the structure represented by Formula I,X and Z are 1-pyrenylmethyl, Y is a 2,9-diazaperopyrenium dication; n is8; all of the R₁ groups are H atoms, all of the R₂, R₃, and R₄ groupsare OH groups, and C⁻ of the rotaxane-type dyes is Cl⁻.

A detailed description of methods for making a fluorescent dye havingthe structure represented by Formula I is provided in the Examples andthe Appendix to this example. Briefly, one embodiment of the methodscomprises reacting one or more dye molecules that comprise one or morepropargyl ammonium/pyridinium groups, another one or more dyes thatcomprise one or more azido ethyl ammonium/pyridinium groups,cyclodextrin, and cucurbit[6]uril in water at a temperature between 0°C. and 100° C. By way of illustration, N-(1-pyrenyl methyl)-N-propargylammonium chloride, 2,9-bis(2-azidoethyl)-2,9-diazaperopyrenium chloride,γ-cyclodextrin, and cucurbit[6]uril can be reacted in water at 60° C.This reaction is shown in FIG. 1A.

The heterorotaxane dye compounds are characterized in that they undergoaggregation in aqueous solution, the extent of which depends on theirconcentration in the solution, the temperature of the solution and theirchemical environment. Therefore, because the fluorescence emissionspectra for the dye solutions, and for inks printed from the solutions,is dependent on the extent of dye aggregation, the fluorescence emissionspectra can be altered by manipulating the equilibrium between themonomeric and aggregated states of the heterorotaxane dyes. This isillustrated schematically in FIG. 1B. In the present ink compositions,this equilibrium is manipulated by the use of one or more encapsulatingagents and one or more competitive binding agents in aqueous inkcompositions. This is illustrated schematically in FIG. 2A.

The encapsulating agents are molecules comprising a macrocyclic ringthat is capable of encapsulating one or both of the fluorophoric endgroups on the substantially linear molecule of the heterorotaxane. Assuch, the presence of the encapsulating agents promotes the monomericstate of the fluorescent dyes. The encapsulating agents can befluorophoric molecules or non-fluorophoric molecules. The macrocyclicring may be, for example, the same type of macrocyclic ring thatencircles the central fluorophoric group of the heterorotaxane. By wayof illustration, if the central fluorophoric group of the heterorotaxaneis encircled by a cyclodextrin (CD) ring, the encapsulating agent may beγ-CD. Although it is not necessary to include an encapsulating agent inthe ink compositions, their inclusion makes it possible to formulate inkcompositions having a wide range of fluorescent colors for printingpolychromic images. This wide color range can be achieved by includingthe encapsulating agents even if the ink compositions all comprise thesame fluorescent dye molecules.

The competitive binding agents are molecules that compete with thefluorophoric end groups for binding to the encapsulating agents. Assuch, the inclusion of the competitive binding agents in the inkcompositions promotes the aggregated state of the fluorescent dyes. Thecompetitive binding agents can be fluorophoric molecules ornon-fluorophoric molecules. In some embodiment of the ink compositions,the competitive binding agents comprise the same fluorophoric groups asthe heterorotaxane. By way of illustration, if the encapsulating agentcomprises a CD ring, the competitive binding agent may be2-adamantylamine hydrochloride. However, many other competitive bindingagents can be used. The competitive binding agents need not be includedin the ink compositions. However, when they are present in combinationwith one or more encapsulating agents, they enable the ink compositionsto access an even wider range of fluorescent colors.

The fluorescence intensity of the ink compositions and inks at a givenwavelength will be determined by the sum of the fluorescence emissionintensities of each component in the ink composition or printed ink.Thus, at a given wavelength, the fluorescence intensity of the inkcompositions and printed inks printed from the compositions will dependon the relative concentrations of the components of the ink compositionsand will also depend on the association strength between theencapsulating agents and the competitive binding agents. Moreover,because the sensitivity of the fluorescence emission spectra to theconcentrations of the components and their equilibrium constants isnon-linear, the complex supramolecular equilibria in the aqueous inkcompositions give rise to a powerful chemical encryption printing systemcharacterized by a complex and highly varied printed color palette. As aresult, multicolored fluorescent images can be produced by applyingdifferent ink compositions to the surface of a substrate and allowingthe inks to dry, providing a polychromatic film of ink on the surface.The different ink compositions may differ in the relative amounts ofheterorotaxane, encapsulating agent and binding agent present insolution, differ in the competitive binding agents present in solution,or differ in both respects.

The multicolored fluorescent images can be printed using an automatedprinting device, such as an inkjet printer, comprising a plurality ofink channels containing the different ink compositions. However, the inkcomposition can also be dispensed from handheld writing utensils, suchas ink pens. When the ink compositions dry they form an image thatappears multicolored when viewed under an ultraviolet light.

The presence of the inks in a printed image can be verified by simplyviewing the image under an appropriate light source, such as a UV lightsource and observing the resulting fluorescence emission from the image.Further confirmation of the presence of the inks can be verified usingchemical indicators. Indicators that the inks are present in a printedimage include: the observation of a non-linear color change when theprinted image is exposed to aqueous solutions containing differentcompetitive binding agents; the observation of a change in the colorgradient of the image or the observation of new colors in the image whena composition comprising a competitive binding agent and/or anencapsulating agent is printed over the printed image; the observationof a characteristic color change when the printed image is exposed to afluorescence quencher; and/or the observation of a characteristic colorchange when the printed image is submerged in water or an aqueoussolution.

Similarly, the authenticity of a printed image comprising thefluorescent inks can be verified by applying an authentication reagentover the image, wherein the authentication reagent induces a change inthe fluorescence emission spectrum of the image; and comparing thechange in the fluorescence emission spectrum of the image against aknown fluorescence emission spectrum change for an authentic printedimage. That is, the change in the emission spectrum can be comparedagainst a known standard. The printed image being authenticated may bepolychromic image. The comparison may be carried out by simply comparinga visual observation of the change in the fluorescence emission with anexpected change in the fluorescence emission. Alternatively, thefluorescence emission spectrum of the image can be obtained under UVillumination before and after the application of the authenticationreagent to obtain the change in the emission spectrum for the printedimage. That change can then be compared with the change in thefluorescence emission spectrum for an authentic printed image, using thesame authentication reagent, to see if they match.

Various embodiments of the authentication reagents operate as follows.In some embodiments the authentication reagents comprise water-solublenon-fluorescent encapsulating agents and/or non-fluorescent competitivebinding agents that alter the fluorescence emission spectrum of theimage. In other embodiments, the authentication reagents comprisewater-soluble fluorescent dyes as competitive binding that alter thefluorescence emission spectrum of the image. In still other embodiments,the authentication reagents comprise salts that provide anions thatundergo anion exchange with the anions associated with theheterorotaxane in the fluorescent inks to alter the fluorescenceemission spectrum of the image. In yet other embodiments, theauthentication reagent comprises water, which washes away water-solubleencapsulation agents and/or water soluble competitive binding agents inthe fluorescent inks to alter the fluorescence emission spectrum of theimage.

The use of the fluorescent dyes to print and authenticate a polychromicimage is illustrated in the flowchart of FIG. 4C. Initially an inkcomposition color palette can be generated from a plurality of inkcompositions characterized by different fluorescent emission spectra,depending upon the particular formulation of each ink composition. Anumber of the ink compositions from the color palette can then beselected for printing. Information about the nature and concentration ofthe components in each of the selected ink compositions issupramolecularly encrypted into characteristic fluorescent emissionspectra that depend, in a non-linear fashion, on the concentration offluorescent dye present in the ink composition and also on the natureand concentration of encapsulating agents and competitive binding agentsin the ink composition. The selected ink compositions are then printedonto a substrate to form a polychromic image comprising the fluorescentdyes, thereby encrypting the fluorescence emission spectra informationin the printed image. Finally, the authenticity of the printed image canbe verified using a chemical authentication agent, as described above.

EXAMPLES

These examples illustrate a class of amorphous solid-state fluorescentmaterials that (i) can be printed as aqueous ink compositions, with amodular supramolecular encryption motif which (ii) provides access tobroad-spectrum fluorescent color palettes that (iii) are inherentlydifficult to reverse engineer, and which (iv) respond rapidly tocolor-changing chemical authentication. In this example R4.4Cl is theheterorotaxane, γ-CD is used as an encapsulating agent, and Ad.Cl,AdMe.Cl or PyMe.Cl are used as a competitive binding agents.

The key dye compound is a heterorotaxane R4.4Cl, which can besynthesized (FIG. 1A) from cucurbit[6]uril (CB6), γ-cyclodextrin (γ-CD)and two fluorescent precursors, one (1.Cl) derived from pyrene and theother (2.2Cl) from a diazaperopyrenium (DAPP) dication. The efficient(83%) and rapid (˜3 h) production (16) of R4.4Cl in water is facilitated(17, 18) by cooperative capture. It was initially envisioned that theCB6 and γ-CD rings in this heterorotaxane could preventaggregation-induced quenching of the DAPP fluorophore, which exhibits(19) a high fluorescence quantum yield in solution (Φ=53%) but not inthe solid state (Φ≈0).

In its UV/Vis absorption spectrum (FIG. 1B), R4.4Cl has twocharacteristic absorption bands at 341 and 443 nm, which can beattributed (19) to electronic transitions in the pyrenyl and DAPP units,respectively. Despite the presence of the CB6 (20) and γ-CD rings (21),R4.4Cl is driven by intermolecular hydrophobic and π-π stackinginteractions to form aggregates (R⁴⁺agg) in water. A blue shift (7 nm)of the absorption band near 450 nm was recorded (FIG. 1D) in theconcentration-dependent UV/Vis absorption spectrum of R4.4Cl upondilution from 500 to 25 μM, while the shoulder around 350 nm, arisingfrom the pyrene stopper, diminished. Assuming that aggregation ishomogenous and non-cooperative (22), the aggregation constant K_(agg)(23) was determined to be 1.6×10⁴ M⁻¹. Irradiating the monomeric R4.4Cl(5 μM) at 340 and 443 nm resulted in identical fluorescence emissionspectra with an emission maximum (Φ=52.4%) at 510 nm. No emission wasobserved at 390 nm, indicating (FIG. 1C) the transfer of the excitedstate energy from pyrene to DAPP by a Förster resonance energy transfer(FRET) mechanism (24) with near-quantitative (>99%) efficiency.

As R4.4Cl undergoes increased aggregation at higher and higherconcentrations, its narrow emission band (FIG. 1E) at 510 nm wasgradually replaced by a broad, featureless band around 610 nm, implyingthat either excimers (DAPP homodimers) or exciplexes (pyrenyl-DAPPheterodimers) are being formed in the excited state. Circular dichroismspectra reveal (FIG. 1F) that the aggregation of R4.4Cl (200 μM) istemperature dependent. As the temperature was lowered from 80° C.(monomeric state) to 2° C. (aggregated state), the positive inducedcircular dichroism (ICD) signals diminished as a negative ICD peak,attributable to the pyrene stoppers, appeared at around 350 nm,indicating (25, 26) that these stoppers congregate near the rims of theγ-CD ring. Since γ-CD encircles DAPP, it follows that pyrene-DAPPheterodimers (FIG. 1B), and their corresponding exciplexes, areresponsible for the observed aggregation and emission behavior ofR4.4Cl.

The equilibrium (FIG. 2A) between monomeric and aggregated states ofR4.4Cl can be manipulated by chemical means. Assuming that aggregationis non-cooperative, the R⁴⁺ ₂ dimer can be considered (22) as asimplified case of R⁴⁺ _(agg), in which K_(agg)=¼[R⁴⁺ ₂].[R⁴⁺]⁻².Encapsulation of the pyrene stoppers by γ-CD promotes the disassembly ofR⁴⁺ ₂ in favor of a monomeric R⁴⁺⊂γ-CD₂ complex, formed from a R⁴⁺⊂γ-CDintermediate, with an equilibrium constant K_(CD)═K₁.K₂. Thisdisassembly process can be reversed by introducing a competitive bindingagent (CA) which competes for γ-CD in solution with an associationconstant, K_(CA). Combining these equilibria, the system is described by

$\begin{matrix}{{{{R\; 4^{4 +}} + {3C\; D} + {CA}}\overset{4{K_{agg} \cdot K_{CD} \cdot K_{3}}}{\rightleftharpoons}{{R4}_{2}^{4 +} + {R4}^{4 +}}} \Subset {{CD}_{2} + {CA}} \Subset {CD}} & \left( {{Eq}.\mspace{14mu} 1} \right) \\\; & \;\end{matrix}$

Since K_(agg) and K_(CD) are fixed for R4.4Cl, these equilibria aresensitive to four variables—namely, the initial concentrations (i.e.,[R⁴⁺]₀, [CD]₀, and [CA]₀) of each component and K_(CA). In an aqueoussolution containing R4.4Cl, γ-CD and CA, the fluorescence intensityI_(λ) at a given wavelength λ is the sum of the emission intensities ofeach component, which is given by

I_(λ)═F_(R4) ₄₊ ^(o)[R4⁴⁺]+F_(R4) ₂ ^(o)[R4₂ ⁴⁺]+F_(R4) ₄₊ _(⊂CD)^(o)[R4⁴⁺⊂CD]+F_(R4) ₄₊ _(⊂CD) ₂ ^(o)[R4⁴⁺⊂CD₂]+F_(CD) ^(o)[CD]+F_(CA)^(o)[CA]+F_(CA⊂CD) ^(o)[CA⊂CD]  (Eq. 2)

where F^(o) is the molar fluorescence coefficient at wavelength λ. Notethat the use of a non-fluorescent CA such as 2-adamantylaminehydrochloride (Ad.Cl; K_(CA)=90 M⁻¹) simplifies Eq. 2, since, in thisinstance, the terms F^(o) _(CA)[CA] and F^(o) _(CA⊂CD)[CA⊂CD] arereduced to zero. Combining this simplified form of Eq. 2 with Eq. 1,

I_(λ)═F_(R4) ₄₊ ^(o)+F_(R4) ₄₊ _(⊂CD) ^(o).√{square root over(K_(CD))}([CD]₀−3m)+F_(R4) ₄₊ _(⊂CD) ₂^(o).K_(CD).([CD]₀−3m)².([R4⁴⁺]₀−3m)+F_(R4) ₂ ₄₊^(o).4K_(agg).([R4⁴⁺]₀−3m)²  (Eq. 2)

where m is the molar concentration of CA being encapsulated by γ-CD.Knowledge of the initial concentrations and equilibrium constants allowsEq. 3 to be solved.

The solid-state fluorescence outputs (FIGS. 2B and 2C) of R⁴⁺ and R⁴⁺⊂γ-CD₂ reflect their solution outputs. Emission from amorphous mixturesof R4.4Cl:γ-CD ranged (FIG. 2C) from λ_(max)=610 nm (Φ=7.7%) with noγ-CD (R⁴⁺ agg) to 510 nm (Φ=42.5%) in the presence of 200 equiv of γ-CD(R⁴⁺ ⊂CD₂). Solid-state emission was also conserved from solution when[CA] was non-zero. For example, the addition of 200 equiv of Ad.Cl to amixture comprising R4.4Cl:γ-CD (molar ratio: 1:200) resulted in ared-shift (FIGS. 2B and 2C) of the emission back to λ_(max)=580 nm.Thus, the ratio of R4.4Cl, γ-CD, and Ad.Cl can be used, as described byEq. 3, to tune the solid-state fluorescence reversibly over a wide colorrange from green through to red.

Since R⁴⁺-based aqueous solutions are compatible with both handwritingand inkjet printing technologies, they can be applied (FIG. 3) asfluorescent inks. We found that the R⁴⁺ ⊂CD₂ ink exhibits an unusualphenomenon—the color of its emission depends (FIG. 3A) on the type ofpaper used as a result of varying noncovalent interactions with papersof different compositions. Under UV light, R4.4Cl appears reddish-orangeand R⁴⁺ ⊂CD₂ appears green on rag paper, newsprint, and banknotes,consistent with the corresponding powders, whereas, on various types ofordinary white paper (FIG. 3A and Table 1), both of these inks appearreddish-orange. A monochromic QR code (FIG. 3B) printed on paper from aninkjet cartridge contains information that, although invisible undernatural light, can be read on a smartphone under UV light. By loadingaqueous solutions of R⁴⁺ ⊂CD₂ (R⁴⁺: γ-CD=1:50), γ-CD, and Ad.Cl into atri-color inkjet cartridge (FIG. 3C), polychromic fluorescence printingis possible, provided that the rates of supramolecular encapsulation arefaster than the rates of printing and drying. A fluorescent reproductionof van Gogh's ‘Sunflowers’ and its digital replica (FIG. 3D and FIG. 3E,respectively) demonstrate the feasibility of printing broad-spectrumpolychromic images with good color resolution. It is worth noting thatR⁴⁺ is well-placed for assimilation into a commercial setting on accountof its simple and high-yielding synthesis from commodity chemicals. Afluorescent replica of Briex's ‘Apostelhoeve Wine Estate Maastricht’printed using an inkjet cartridge with the same setting as in FIG. 3Kunder UV and natural light and its digital replica are shown in FIGS. 3Land 3M, repectively.

At a fundamental level, the nonlinear nature of this system'ssensitivity to concentrations of components and their equilibriumconstants (Eq. 3) points towards a general concept whereby complexsupramolecular equilibria in aqueous solution can be used as a chemicalencryption method. Even with access to all of the ink components, itwould be challenging for counterfeiters to reproduce a printed colorpalette without having a complete knowledge of the inks' initialconcentrations and channel assignments in the print cartridge. In anattempt to demonstrate the non-linear nature of this system, we haveprinted fluorescent color palettes (FIGS. 3G-3J) using various inkconcentrations and different CAs. (A standard color palette is shown inFIG. 3F.) A broad range of colors from green to red were printed (FIG.3G) when Ad.Cl was used as the competitor. The color palette was alsosensitive to the association strength of the competitor, noting thedifferences between images printed from equally concentrated solutionsof Ad.Cl (FIG. 3G) and a stronger-binding competitor (FIG. 3H), namely,1-adamantanemethylamine hydrochloride (AdMe.Cl, K_(AdMe)=127 M⁻¹).Reducing the concentrations of either CA (FIGS. 3H and 3I) or γ-CD(FIGS. 3H and 3J) contracts the color spectrum in the greenish-yellowregion or yellowish-red region, respectively. The color range of thefluorescent inks can be expanded to accommodate RGB printing (FIG. 3K)by choosing a fluorescent CA, such as a fragment of the R4.4Cl,1-pyrenemethylamine hydrochloride (PyMe.Cl), with blue emission. Theability to exchange fluorescent and non-fluorescent CAs in a modular anduser-controlled manner elevates the anti-counterfeiting featurespossessed intrinsically by this security ink.

The dynamic nature of the inks makes them amenable to a variety (FIG. 4)of fraud detection tests. Exposure of a printed image (FIG. 4A) toaqueous solutions of different CAs results (Eq. 3) in nonlinear colorchanges. Printing non-fluorescent AdMe.Cl or CD on top of an existingdocument changes the existing color gradient of the image, whileprinting fluorescent PyMe.Cl or 1,3,6,8-pyrenetetrasulfonic acidtetrasodium (PTSA.4Na) creates new colors such as blue and purple byshifting the complex equilibria or extent of counterion exchange. Acharacteristic color change can also be brought about through theapplication of a quencher, such as tryptophan, or even by simply soakingthe printed image in water for as little as 1-2 mins, during which timeγ-CD and the CA will be washed away. Not only can these authenticationagents discriminate between images produced by the R⁴⁺-based ink andother dyes, but they can also distinguish those produced using differentink formulations containing R⁴⁺. Blocks of a given fluorescence color(FIG. 4B, lanes 1b-c and 2b-c), which appear almost identical to oneanother under UV light, but are formulated differently, were found toresult in noticeably different colors (FIGS. 4B, lanes 1a, 1d, 2a, and2d) after the application of the same amount of an authentication agent.Since hundreds of chemicals meet the criteria to be competing agents, inprinciple we can generate an infinite library of different ink systemsand authentication tests using this supramolecular encryption method. Aflow chart of the authentication process is shown in FIG. 4C.

We have developed a stimulus-responsive solid-state fluorescentheterorotaxane, prepared from simple materials using a cooperativecapture method, and applied it as a component of fluorescent securityinks. The solid-state emission of these security inks can be fine-tunedover a wide emission range with rapid response to chemical stimuli. Theprinted information is encrypted in a chemical language based on anonlinear equation that describes a dynamic network, which can generatea potentially infinite library of different fluorescent color palettes.In contrast with conventional dyes, the encrypted information printedwith the heterorotaxane inks can be verified using chemicalauthentication without revealing the original color image information.

Materials and Methods

All reagents were purchased from commercial suppliers (Aldrich, Fisherand Wacker) and used as received. Thin layer chromatography (TLC) wasperformed on silica gel 60 F254 (E. Merck). Column chromatography wascarried out on silica gel 60F (Merck 9385, 0.040-0.063 mm). UV/VisAbsorption spectra were measured on a Shimadzu 3600 UV/Vis/NIRspectrometer with a temperature control system, employing cuvettes withpath lengths of 1 and 10 mm. Steady-state fluorescence spectra of liquidsamples were measured on a Horiba FluoroMax-4 spectrofluorometer.Steady-state fluorescence spectra of solid samples were measured on anISS PCl Fluorimeter. Absolute fluorescence quantum yields were measuredon a Horiba FluoroMax-4 spectrofluorometer with a Quanta-φ integratingsphere attachment, and the resulting data were analyzed by the 4-curvemethod using the FluorEssence 3.5 software. Circular dichroism spectrawere measured on a Jasco J-815 Circular Dichoism spectrometer with atemperature control system. Dynamic light scattering data were obtainedon a Malvem Zetasizer Nano with a 633 nm He—Ne laser light source.Nuclear magnetic resonance (NMR) spectra were recorded on Bruker Avance500 or 600 spectrometers with working frequencies of 500 or 600 MHz for1H and 125 or 150 MHz for 13C nuclei, respectively. Low-resolutionelectrospray ionization mass spectra (ESI-MS) were recorded on either anAgilent 1100 MSD or a Thermo Finnegan LCQ instrument. High-resolutionelectrospray ionization mass spectra (HR-ESI-MS) were recorded on anAgilent 6210 LC-TOF instrument with Agilent 1200 HPLC introduction.Writing tests were performed using Pilot Parallel pens, which werefilled with customized ink cartridges. Printing tests were performedusing a HP Photosmart CP4780 inkjet printer with HP60 black and tricolorink cartridges, which were filled with customized inks.

Synthetic Protocols Synthesis of 1.Cl

1.Cl (27): 1-Pyrenecarboxaldehyde (2.00 g, 8.69 mmol) was dissolved inCH₂Cl₂/MeOH (v/v, 4:1, 50 mL) and propargylamine (0.62 mL, 9.6 mmol) wasadded to the solution. The reaction mixture was heated under reflux inan atmosphere of nitrogen for 18 h. After all the 1-pyrenecarboxaldehydehad been consumed (monitored by TLC), the reaction mixture was cooled to0° C. then NaBH₄ (1.50 g) was added in portions to the reaction mixture.After stirring for 6 h, an aqueous HCl solution (37% w/w, 6 mL) wasadded to quench the excess of NaBH₄ in the reaction mixture. The solventwas removed under reduced pressure and then an aqueous 2 M NaOH solution(50 mL) was added. The reaction mixture was extracted with CH₂Cl₂ (3×100mL) and the organic phase was dried (Na₂SO₄). The CH₂Cl₂ solution waspurged with an excess of HCl gas (HCl gas was generated by addingsaturated aqueous HCl solution to anhydrous CaCl₂), whereuponprecipitation occurred. The precipitate was collected by filtration andwashed with an excess of CH₂Cl₂ to afford 1.Cl as a light yellow powder(1.10 g, 41%).

Synthesis of 2.2Cl

S2: Compound S2 was synthesized using a protocol based on a previouslyreported procedure (28) with slight modifications. Compound S1 (0.50 g,1.12 mmol), 2-azidoethylamine (29) (1.46 g, 17.0 mmol) and K₂CO₃ (1.00g, 7.24 mmol, anhydrous) in anhydrous THF (50 mL) was heated underreflux in an atmosphere of nitrogen for 48 h. The solvent was thenremoved under reduced pressure and the residue was purified by columnchromatography (SiO₂, gradient CH₂Cl₂-10% Me₂CO in CH₂Cl₂ (m/v), Rf=0.4)to afford the product S2 as an orange-yellow powder (402 mg, 76%).Caution: In the previously reported procedure, (3) simple washing by H₂Oand Et₂O is not sufficient to remove all the byproducts of the reaction.The product S2, purified after column chromatography, is highly solublein common organic solvents.

2.2Cl: The diazide 2.2Cl was synthesized based on a previously reportedmethod (30) with slight modifications. Compound S2 (0.50 g, 1.06 mmol)and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in anhydrousdegassed MeCN (80 mL) was heated under reflux in an atmosphere ofnitrogen for 18 h. The reaction mixture was cooled to room temperature,followed by adding 6 m of aqueous HC solution (37 of tetrabutylammonw/w), which generated a precipitate. This precipitate was collected byfiltration and washed with 1:1 Et₂O/MeCN (4×50 mL) to afford a crudeproduct as a dichloride salt. The impurities in the crude product wereremoved effectively by initiating two cycles of a counterion exchangeprocedure. Firstly, an excess of NH₄PF₆ was added to the aqueoussolution of the crude product in order to exchange the counterion fromCl⁻ to PF₆ ⁻ and generate 2.2PF₆ as an orange precipitate. Theprecipitate was collected by filtration and washed with an excess ofH₂O. The second counterion exchange process involved adding a largeexcess of tetrabutylammonium chloride (TBACl) to a MeCN solution of2.2PF₆. The precipitate which formed was collected by filtration andwashed with an excess of MeCN to afford pure 2.2Cl as a dark yellowpowder (455 mg, 80%).

Synthesis of [3]Rotaxane R3⁴⁺ and [4]Rotaxane R⁴⁺

General Procedure for the Synthesis of [3]Rotaxane R3⁴⁺ and the[4]Rotaxane R⁴⁺.

The stopper precursor 1.Cl (2.2 equiv), the dumbbell precursor 2.2Cl(1.0 equiv), and γ-CD (2.5-20 equiv) were mixed in H₂O and stirred at60° C. for 10 min before CB6 (2.5 equiv) was added. The reaction mixturewas stirred at 60° C. for a further 18 h. Afterwards, insoluble residueswere filtered off from the reaction mixture and an excess of NH₄PF₆ wasadded to the filtrate. The precipitate which formed was collected byfiltration and washed with an excess of H₂O. This mixture of productswas dissolved in MeCN and subjected to reverse-phase analytical HPLCanalysis (C18 column, 5 μm packing, length 150 mm, diameter 4.6 mm,eluent: 0 min 0.1% TFA in H₂O 99.9% to 40 min 0.1% TFA in 99.9% MeCN,flow rate: 1 mL/min). An excess of Bu₄NCl was added to this MeCNsolution to ensure that all the counterions were exchanged to Cl⁻ ions.The precipitate which formed was collected, washed with an excess ofMeCN and purified on a reverse-phase C18 column (150 gram, RediSep RfGold C18Aq) on an automatic column chromatography system (CombiflashRf200, Teledyne Isco, eluent: H₂O/MeCN (0.1% TFA)=100/0 to 0/60 in 40mins, flow rate: 85 mL/min) to afford R3⁴⁺ and R⁴⁺ as their TFA salts.The appropriate fractions containing R3⁴⁺ were collected and thecounterion of the R3⁴⁺ was exchanged first of all to PF₆ ⁻ on additionof an excess of NH₄PF₆ to the collected fractions. After removal of MeCNunder reduced pressure, the product R3.4PF₆ (3-41%) precipitated outfrom the solution and it was collected by vacuum filtration withextensive washing with H₂O.

The [3]rotaxane R3.4Cl was obtained after a second counterion exchangeprocedure wherein an excess of Bu₄NCl was added to a MeCN solution ofR3.4PF₆, resulting in the formation of a precipitate, which wascollected by vacuum filtration, washed with excess of MeCN and driedunder vacuum to afford R3.4Cl (2-39%) as an orange powder.

Optimized Synthesis of the Hetero[4]Rotaxane R4.4Cl.

The stopper precursor 1.Cl (67 mg, 0.22 mmol), the dumbbell precursor2.2Cl (54 mg, 0.10 mmol), and γ-CD (1287 mg, 1.00 mmol) were mixedtogether in H₂O (35 mL) and stirred at 60° C. for 10 min before CB6 (250mg, 0.25 mmol) was added. The reaction mixture was stirred for a further3 h at 60° C. Thereafter, the insoluble residues were filtered off fromthe reaction mixture. The filtrate was loaded directly onto areverse-phase C18 column (150 gram, RediSep Rf Gold C18Aq) on anautomatic column chromatography system (Combiflash Rf200, Teledyne Isco)(eluent: H₂O/MeCN (0.1% TFA)=100/0 to 0/60 in 40 mins, flow rate: 85mL/min). The appropriate fractions containing R⁴⁺ were collected and thecounterion of the R⁴⁺ was exchanged to PF₆ ⁻ on addition an excess ofNH₄PF₆ to the collected fractions. After removal of MeCN under reducedpressure, the product R4.4PF₆ (416.4 mg, 85%) precipitated out from thesolution: it was collected by vacuum filtration with extensive washingwith H₂O.

The [4]rotaxane R4.4Cl was obtained after a second counterion exchangeprocedure wherein an excess of Bu₄NCl was added to a MeCN solution ofR4.4PF₆, resulting in the formation of a precipitate, which wascollected by vacuum filtration, washed with excess of MeCN and driedunder vacuum to afford R4.4Cl (371 mg, 83%) as an orange powder.

TABLE 1 Yields of the hetero[3]rotaxane R3•4Cl and the hetero[4]rotaxaneR4•4Cl synthesized from precursors 1•Cl (2.2 mM) and 2•2Cl (1 mM), CB6and γ-CD at various temperatures. Tem- pera- ture 1•Cl 2•2Cl CB6 γ-CDYield/% Entries (° C.) (Equiv) (Equiv) (Equiv) (Equiv) R3•4Cl R4•4Cl 1 02.2 1.0 2.5 10  2^(a) 12^(a) 2 20 2.2 1.0 2.5 10  8^(a) 48^(a) 3 40 2.21.0 2.5 10 21^(a) 71^(a) 4 60 2.2 1.0 2.5 2.5 39^(b)  9^(b) 5 60 2.2 1.02.5 5 24^(b) 21^(b) 6 60 2.2 1.0 2.5 10 11^(a) 88^(a) 7 60 2.2 1.0 2.510  8^(b) 83^(b) 8 60 2.2 1.0 2.5 20 17^(b) 56^(b) 9 80 2.2 1.0 2.5 1016^(a) 81^(a) ^(a)Yields estimated by the integration of thecorresponding peaks in the reverse-phase analytical HPLC traces.^(b)Isolated yields.

The stopper precursor 1.Cl (110.2 mg, 0.36 mmol), the dumbbell precursor3.2Cl (50.7 mg, 0.12 mmol), and γ-CD (272.6 mg, 0.36 mmol) were mixed inH₂O (50 mL) and stirred at 60° C. for 10 min before CB6 (359.2 mg, 0.24mmol) was added. The reaction mixture was stirred at 60° C. for afurther 3 h. Thereafter, the insoluble residues were filtered off fromthe reaction mixture. The filtrate was loaded directly onto areverse-phase C18 column (150 gram, RediSep Rf Gold C18Aq) on anautomatic column chromatographic system (Combiflash Rf200, TeledyneIsco) in order to isolate the desired product (eluent: H₂O/MeCN (0.1%TFA)=100/0 to 0/60 in 40 mins, flow rate: 85 mL/min). The appropriatefractions containing SR⁴⁺ were collected, and the solvent was removedunder reduced pressure. The residue was dissolved in MeNO₂, and thecounterion of the SR⁴⁺ was exchanged to Cl⁻ on addition of an excess oftetrabutylammonium chloride. The resulting white precipitate wascollected by vacuum filtration, washed with an excess of MeNO₂ and driedunder vacuum to afford SR4.4Cl (464.3 mg, 93%) as a white powder.

Isothermal Titration Calorimetry (ITC) Studies on 2.2Cl with γ-CD

Sample Preparation: 2.2Cl (1.8 mg) was dissolved in H₂O (10 mL) and anexcess of CB6 (14 mg) was added to the solution. The mixture was placedin an ultrasonic bath for 10 min and then passed through a syringefilter (0.25 μm). The generated bright yellow solution of the complex2.2Cl⊂CB6 was then used for ITC.

The heat (dQ/dt) generated during titrations by the complexation between2.2Cl⊂CB6 and γ-CD was too weak to be measured accurately by ITC. Thisresult suggests that the binding constant (Ka) of 2.2Cl⊂CB6 and γ-CD wasbelow the lower limit of the ITC measurement (Ka<50 M⁻¹)

Förster Resonance Energy Transfer (FRET) Studies

The emission of the pyrenyl unit of 1.Cl exhibited a significant overlapwith the absorption of the DAPP unit in 2.2Cl, suggesting that the FRETprocess could take place if the donor 1.Cl and the acceptor 2.2Cl werein close proximity. In the UV-Vis spectrum of an aqueous R4.4Clsolution, characteristic absorption bands attributed to the pyrenyl andDAPP units were observed in the 318-365 and 365-520 nm regions. Theemission spectrum of R4.4Cl was independent of the excitationwavelength, giving identical emission spectra. No pyrenyl unit emissionwas observed at around 350-450 nm. The excitation spectrum of R4.4Cl wassimilar to its UV-Vis spectrum. These results indicate that energytransfer between the pyrenyl and DAPP units takes place with nearquantitative (>99%) efficiency. The simulated structure of R⁴⁺ showedthat the distance between the pyrenyl and DAPP unit is within 10-12 Å.

Quantum Yield Measurements

Absolute fluorescence quantum yields were measured using a HoribaFluoroMax-4 spectrofluorometer with a Quanta-φ integrating sphereattachment. Data were analyzed by the 4-curve method using theFluorEssence 3.5 software. Typically, the quantum yield was calculatedby

$\phi = \frac{E_{s} - E_{b}}{L_{b} - L_{s}}$

where E_(s) is the integrated fluorescence profile of the sample causedby direct excitation, E_(b) is the integrated fluorescence profile of anempty integrating sphere (without the sample, only a blank), L_(b) isthe integrated Rayleigh excitation peak of an empty integrating sphere(only a blank), and L_(s) is the integrated Rayleigh excitation peak ofthe sample when it is directly excited by the incident beam.

When acquiring the sample and blank fluorescence profiles, the number ofaccumulated scans was increased from 1 to 20 summed scans on account ofthe weak emission in comparison to the strong Rayleigh scattering. Thisfactor of 20 was accounted for in the calculation of the quantum yieldby dividing (E_(s)−E_(b)) by 20.

TABLE 2 Quantum yields of samples in this study in both aqueoussolutions and solid state measured at room temperature. Quantum Yield Φ= (%) Solution Solid State 1•Cl 22.8 ± 0.25  4.0 ± 0.01 2•2Cl 51.3 ±0.36  0.1 R3•4Cl 18.3 ± 0.11  1.7 ± 0.01 R3⊂CD complex 1:200 25.9 ± 0.04R4•4Cl 52.4 ± 0.27  7.7 ± 0.01 R4⊂CD complex R4:CD = 1:5 10.4 ± 0.021:20 12.1 ± 0.02 1:35 15.7 ± 0.03 1:50 19.6 ± 0.03 1:75 25.8 ± 0.031:100 31.0 ± 0.05 1:150 36.9 ± 0.06 1:200 45.7 ± 0.08 1:200 +200 Ad•Cl15.4 ± 0.03

Additional Details Regarding Supramolecular Encryption Theory

When mixing inks from each channel in the tri-color inkjet cartridge,the color of the printed dot is dependent to the amount of each inkdeposited on the paper surface. In the tri-color inkjet cartridge, theaqueous solutions of the [4]rotaxane R4.4Cl/γ-CD, γ-CD and Ad.Cl wereloaded separately into three channels. In an initial experiment, wechose Ad.Cl and AdMe.Cl as non-fluorescent competitors to participate inthe supramolecular equilibrium network. Thus, when the competitor isnon-fluorescent, the aggregation equilibrium of the [4]rotaxane R4.4Clin solution or in the solid state can be described using Eq. A.

$\begin{matrix}{{R\; 4}\overset{K_{a\; 1}}{\rightleftharpoons}{R\; 4_{2}}\overset{K_{a\; 2}}{\rightleftharpoons}{R\; 4_{3}}\overset{K_{a\; 3}}{\rightleftharpoons}{R\; 4_{4}\mspace{14mu} \ldots}\overset{K_{a\; {({n - 1})}}}{\rightleftharpoons}{R\; 4_{n}}} & \left( {{Eq}.\mspace{14mu} A} \right)\end{matrix}$

If the aggregation of the [4]rotaxane R4.4Cl is homogenous and there isno cooperativity during the nucleation process, the aggregation processcan be simplified as:

$\begin{matrix}{{{nR}\; 4}\overset{n^{n}K_{agg}^{n - 1}}{\rightleftharpoons}{R\; {4_{n}.}}} & \left( {{Eq}.\mspace{14mu} B} \right)\end{matrix}$

Assuming the extents of aggregation in each step are identical, and so:

K_(a1)═K_(a2)═K_(a3)═ . . . ═K_(a(n-1)).

The process can be simplified as:

$\begin{matrix}{{2R\; 4}\overset{4K_{agg}}{\rightleftharpoons}{R\; {4_{2}.}}} & \left( {{Eq}.\mspace{14mu} C} \right)\end{matrix}$

The aggregation constant

$K_{agg} = {\frac{\left\lbrack {R\; 4_{2}} \right\rbrack}{{4\left\lbrack {R\; 4} \right\rbrack}^{2}}.}$

Adding γ-CD to the [4]rotaxane R4.4Cl affords a stepwise binding event,where the γ-CD and R4.4Cl forms 1:1 and 2:1 complexes sequentially.

$\begin{matrix}{{{{{R\; 4} + {C\; D}}\overset{K_{1}}{\rightleftharpoons}{R\; 4}} \Subset {{{CD} + {CD}}\overset{K_{2}}{\rightleftharpoons}{R\; 4}} \Subset {CD}_{2}}{or}} & \left( {{Eq}.\mspace{14mu} D} \right) \\{{{{R\; 4} + {2{CD}}}\overset{K_{CD}}{\rightleftharpoons}{R\; 4}} \Subset {CD}_{2}} & \left( {{Eq}.\mspace{14mu} E} \right)\end{matrix}$

Upon the addition of Ad.Cl or AdMe.Cl, the encapsulation of thecompetitor by γ-CD can be described as:

$\begin{matrix}{{{{CA} + {CD}}\overset{K_{3}}{\rightleftharpoons}{CA}} \Subset {CD}_{2}} & \left( {{Eq}.\mspace{14mu} F} \right)\end{matrix}$and the binding constant

$K_{3} = {\frac{\left\lbrack {{CA} \Subset {CD}} \right\rbrack}{\lbrack{CA}\rbrack \cdot \lbrack{CD}\rbrack}.}$

At any particular wavelength, the fluorescent emission F can bedescribed as:

F═F_(R4)+F_(R4⊂CD)+F_(R4⊂CD) ₂ +F_(R4) ₂ +F_(CA)+F_(CD)+F_(CA⊂CD).  (Eq.G)

The overall fluorescence color of the printed dot is the integration ofthe fluorescence emission in the visible spectrum ∫_(290 nm) ^(700 nm)F.

If the competitor is not fluorescent, fluorescent emission of theprinted dot at a particular wavelength is given by:

F=F_(R4)+F_(R4⊂CD)+F_(R4⊂CD) ₂ +F_(R4) ₂ .  (Eq. H)

Substituting leads to:

I_(λ)═F_(R4) ^(o)[R4]+F_(R4) ₂ ^(o)[R4₂]+F_(R4⊂CD) ^(o)[R4⊂CD]+F_(R4⊂CD)₂ ^(o)[R4⊂CD₂].  (Eq. I)

In Eq. I, F_(R4) ^(o), F_(R4) ₂ ^(o), F_(R4⊂CD) ^(o), and F_(R4⊂CD) ₂^(o) are the molar emissions of each species.Using Eq. A-I,

I_(λ)═(F_(R4) ^(o)[R4]+F_(R4⊂CD) ^(o).√{square root over(K_(CD))}[CD]+F_(R4⊂CD) ₂ ^(o).K_(CD).[CD]²).[R4]+F_(R4) ₂^(o).4K_(agg). [R4]².

The sum of Eq. D-F affords the overall equilibrium network as:

$\begin{matrix}{{{{3R\; 4} + {3{CD}} + {CA}}\overset{4{K_{agg} \cdot K_{CD} \cdot K_{3}}}{\rightleftharpoons}{{R\; 4_{2}} + {R\; 4}}} \Subset {{CD}_{2} + {CA}} \Subset {{CD}.}} & \left( {{Eq}.\mspace{14mu} K} \right)\end{matrix}$

Assuming m of Ad has been consumed in the reaction, then:

${{4{K_{agg} \cdot K_{CD} \cdot K_{3}}} = \frac{m^{3}}{\left( {\left\lbrack {R\; 4} \right\rbrack_{0} - {3m}} \right)^{3}\left( {\lbrack{CD}\rbrack_{0} - {3m}} \right)^{3}\left( {\lbrack{CA}\rbrack_{0} - m} \right)}},{{{since}\left\lbrack {R\; 4} \right\rbrack} = {\left\lbrack {R\; 4} \right\rbrack_{0} - {3m}}},{{{and}\lbrack{CD}\rbrack} = {\lbrack{CD}\rbrack_{0} - {3{m.}}}}$

Thus, the fluorescent emission of the printed dot:

I_(λ)═F_(R4) ^(o)+F_(R4⊂CD) ^(o).√{square root over(K_(CD))}([CD]₀−3m)+F_(R4⊂CD) ₂^(o).K_(CD).([CD]₀−3m)².([R4]₀−3m+FR42^(o).4Kagg.R40−3m2.

If the competitor is fluorescent, then the fluorescence emission of theprinted dot at certain wavelength can be described as:

I_(λ)═F_(R4) ^(o).[R4]+F_(R4) ₂ ^(o).[R4₂]+F_(R4⊂CD)^(o).[R4⊂CD]+F_(R4⊂CD) ₂ ^(o).[R4⊂CD₂]+F_(CA) ^(o). [CA]+F_(CA⊂CD)^(o).[CA⊂CD].

I_(λ)═F_(R4) ^(o)+F_(R4⊂CD) ^(o).√{square root over(K_(CD))}([CD]₀−3m)+F_(R4⊂CD) ₂^(o).K_(CD).([CD]₀−3m)².([R4]₀−3m+FR42^(o).4Kagg.R40−3m2+FCA^(o).CA0−m+FCA⊂CD^(o).m.

Ink Writing Tests

Four type of inks for pen writing were prepared using R4.4Cl (0.5 mM),Ad.Cl (100 mM), γ-CD (100 mM) and R4⊂γ-CD₂ (R4.4Cl=0.5 mM, γ-CD=100 mM)solutions, respectively. Typically, 0.5 mL of the ink was loaded into afountain pen for writing tests. A wide selection of paper-based printingmedia were tested, including copy papers (variety brands and models),matte presentation paper (HP), glossy presentation paper (HP), resumepapers (25 and 100% cotton), newsprint papers, rag paper (100% cotton,without optical brightener), cardboard, and cigarette rolling paper.Banknote identification tests were performed on genuine or counterfeitbanknotes of US Dollars, British Pounds Sterling, Euros, Chinese Yuanand Japanese Yen. In these tests, the corresponding currency symbols ($,£,

, and ¥) were drawn on the banknotes using the fountain pen filled withR4⊂γ-CD₂ ink. The color of the symbols on fake banknotes quickly changedfrom green to orange under the UV LED light, while the symbols ongenuine banknotes retained their green color. To simulate fakebanknotes, images of the different banknotes were downloaded from theworld wide web. One side of the fake banknotes was printed on differentcopy papers at 200% of its original size for use in the writing tests,after which the fake notes were destroyed.

The paper used in the writing test can generally be divided into twocategories: 1) paper with optical brightener; and 2) paper withoutoptical brightener. Optical brighteners have been widely used in thepaper industry to make papers look whiter under natural light. Theseoptical brighteners are fluorescent materials which usually absorb lightin the UV region (340-370 nm) and emit blue fluorescence at around420-470 nm. Optical brightener can interfere with the ink performance byreducing the contrast level. The widely used optical brightener includesstilbene derivatives, coumarins, imidazolines, etc. Many of the opticalbrighteners used in the paper industry can be encapsulated by γ-CD,resulting in a fluorescent color change after writing.

TABLE 3 Summary of writing tests using R4⊂γ-CD₂ ink on different media.Writing media Fluorescent color under UV light Copy paper (75 g/m²,Office Depot) Orange Copy paper (75 g/m², Xerox) Orange Copy paper (80g/m², HP) Orange Matte inkjet print paper (120 g/m², HP) Orange Glossyinkjet print paper (120 g/m², HP) Orange Newsprint paper (40 g/m²) GreenRag paper (220 g/m², coated side) Orange Rag paper (220 g/m², uncoatedside) Green Rag paper (320 g/m², coated side) Orange Rag paper (320g/m², uncoated side) Green Filter paper (Whatman) Green Cigaretterolling paper Green Inkjet Photopaper (HP) Green

As shown in Table 3, R4⊂γ-CD₂ ink is very sensitive to the paper media.Papers made of cellulose (rag paper and filter paper) as well as thosemade of plant fibers (newsprint and cigarette rolling paper) do not seemto interact with the R4⊂γ-CD₂ complex. Most of the daily-use copy paperscontain a large number of additives, which include optical brightener,sizing agents, wet strength additive, dry strength additive, coatingagents, etc. It is practically difficult to elucidate which additive(s)interacts with γ-CD, but this phenomenon was observed consistently inall our writing tests. In addition, rag paper with a coated surface wasable to interact with γ-CD in the R4⊂γ-CD₂ ink, resulting in afluorescence color change under UV light.

Ink Printing Tests

Printing tests were performed on a HP inkjet printer (Photosmart CP4780model) with customized ink cartridges. Rag papers (Canson Infinity RagPhotographique, 100% cotton, without optical brightener, nosurface-coating side) were used for the printing tests based on the inkwriting tests.

Ink cartridges for printing test were customized from the HP black andtri-color cartridges (HP60 model). The filled inks were removed from thecartridge and washed extensively with H₂O and EtOH. The aqueoussolutions of R4.4Cl (4 mL, 0.25 mM) and R4⊂γ-CD₂ (4 mL, R4.4Cl=0.25 mM,γ-CD=50 mM) were loaded into two cleaned black ink cartridges,respectively, to perform the monochrome printing tests. In thepolychrome printing tests, the aqueous solutions of Ad.Cl (2 mL, 100mM), R4/γ-CD (2 mL, R4.4Cl=0.25 mM, γ-CD=10 mM) and γ-CD (2 mL, 50 mM)were loaded into the magenta, yellow, and cyan channels of the cleanedtri-color ink cartridge, respectively. Fluorescent color under UV lightwas tuned by controlling the proportion of three inks in the customizedtri-color ink cartridge. In order to index the colors from a digitalinput file for printing with the desired fluorescent ink colors, twocolor palettes were printed using the original tri-color ink-cartridgesand the customized ink cartridges. Translating the fluorescent inkcolors to the correspondent visible color in the standard color palettein the digital input file accurately reproduced the desired fluorescentink colors in the printed documents.

RGB (Red-Green-Blue) Printing

In order to perform RGB printing, PyMe.Cl was selected to provide bluefluorescent emission upon UV irradiation. There are two ways to provideRGB printing, as shown in FIGS. 5A and 5B.

In practice, both of the settings could provide a wide spectrum ofcolors, ranging from purple to red fluorescence upon UV irradiation. Thecolor distributions of the printed images were very different, however,by using these two types of RBG printing settings.

Authentication Experiments

Theory:

Anti-counterfeiting technology and counterfeiting is a continuousbattle. The [4]rotaxane-based security ink provides several ‘keys’ toencrypt the printed image by means of polychromic printing. By employingthese keys, which are (i) the initial concentrations of inks, (ii) thebinding constants, and (iii) the choice of competitor reagents, one caneasily manipulate (iv) the fluorescent color distribution, (v) the colorspectrum width and (vi) the color intensity of the output file. Thesesecurity features embody the first level security of the[4]rotaxane-based security ink.

Benefiting from the rich properties of the [4]rotaxane, we can furtheradd another level of security through a post-printing authenticationprocess. Post-printing a layer of authentication reagent on top of aprinted polychromic image results in further color changes. Even if acounterfeiter could reverse-engineer to match the fluorescence color ofthe original printed polychromic image, reproducing a color-changeprocess of the polychromic fluorescent image is nigh impossible.Firstly, the color changing process is dynamic—depending on the amountof authentication reagents applied—i.e., printed or sprayed onto theimage—the final color distribution will be different. Secondly, thereare more than 10 post-print authentication reagents that can be appliedto give fingerprint-like color changes. They can be used eitherindividually or combined together to verify the suspect product. Thismethod, therefore, creates a large number of color changingcombinations, which can be used to verify the authenticity of thedocument.

Methods.

Aqueous solutions of post-printing reagents were loaded into empty blackinkjet cartridges and test rag paper with a previously printed colorpalette was loaded into the paper tray of an inkjet printer. Ahomogenous layer of the ink was printed across the sheet of rag paper inorder to coat the color palette. Images were taken under UV light(λ=254) in a dark room.

Strategies.

Post-print authentication can be carried out using four differentstrategies, namely, (i) fluorescent color changing using authenticationreagents that are themselves non-fluorescent, (ii) the introduction ofnew colors using fluorescent authentication reagents, (iii) addition ofcounterion exchange reagents, and (iv) washing with water.

(i) Fluorescent Color Change Using Non-Fluorescent AuthenticationReagents.

Post-printing solutions of binding reagents (e.g., γ-CD) or competitors(Ad.Cl, AdMe.Cl, etc.) on top of images results in a characteristiccolor change. For example, post-printing a γ-CD solution on top of anexisting multi-chromic print will cause hypsochromic shifts in thefluorescence emission colors of areas that were initially red, towardsmore green emission, without affecting colors that were initially greenor blue. Post-printing AdMe.Cl solution will affect several colorregions. The solutions of the authentication reagents are transparentand visibly undistinguishable from one another. When performing theauthentication test, a consumer could easily use a spray bottle (forexample, the bottles used to dispense perfumes) to spray theauthentication reagents on top of the printed information and verify thecolor change.

(ii) Fluorescent Color Change by Printing Fluorescent AuthenticationReagents.

Instead of using non-fluorescent compounds to perform the authenticationtest, many water soluble fluorescent dyes can also be used to verify theauthentication of a given document. These fluorescent dyes not only actas a competitor to shift the supramolecular equilibrium, but they alsocontribute to the color intensity and color spectrum width.

(iii) Fluorescent Color Changing by Counterion Exchanging Reagents.

Exchanging the chloride counterions of the [4]rotaxane by the additionof fluorescent or non-fluorescent salts changes the solid-statefluorescence of the printed image. Unlike strategies (i) and (ii), afterthe counterion exchange process, the [4]rotaxane ink is nearly insolublein water, thus fixing the color change.

(iv) Fluorescent Color Changing by Water Washing.

The simplest way to assess the authenticity of a printed image is byrinsing with water. Both the binding reagents (e.g. γ-CD) and thecompetitors (Ad.Cl, AdMe.Cl, etc.) are water soluble, so can be removedeasily by washing. Surprisingly, although the [4]rotaxane ink is watersoluble when first prepared, it stains paper media very strongly and isresistant to aqueous washing. After soaking the printed documents inwater over 24 h, most of the fluorescent color is lost, but the orangeemission from [4]rotaxane still remains.

The word “illustrative” is used herein to mean serving as an example,instance, or illustration. Any aspect or design described herein as“illustrative” is not necessarily to be construed as preferred oradvantageous over other aspects or designs. Further, for the purposes ofthis disclosure and unless otherwise specified, “a” or “an” means “oneor more”.

The foregoing description of illustrative embodiments of the inventionhas been presented for purposes of illustration and of description. Itis not intended to be exhaustive or to limit the invention to theprecise form disclosed, and modifications and variations are possible inlight of the above teachings or may be acquired from practice of theinvention. The embodiments were chosen and described in order to explainthe principles of the invention and as practical applications of theinvention to enable one skilled in the art to utilize the invention invarious embodiments and with various modifications as suited to theparticular use contemplated. It is intended that the scope of theinvention be defined by the claims appended hereto and theirequivalents.

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What is claimed is:
 1. A fluorescent ink composition comprising: (a)water; (b) a heterorotaxane comprising: (i) a substantially linearmolecule comprising a central fluorophoric group, a first fluorophoricend group on one end of the substantially linear molecule, and a secondfluorophoric end group on the opposite end of the substantially linearmolecule; (ii) a first macrocyclic ring encircling the centralfluorophoric group; (iii) a second macrocyclic ring encircling a portionof the substantially linear molecule between the first fluorophoric endgroup and the central fluorophoric group; and (iv) a third macrocyclicring encircling a portion of the substantially linear molecule betweenthe second fluorophoric end group and the central fluorophoric group;and (c) an encapsulating agent comprising a macrocyclic ring that iscapable of encapsulating one or both of the first and secondfluorophoric end groups.
 2. The composition of claim 1, furthercomprising: (d) a competitive binding agent that competes with one orboth of the first and second fluorophoric end groups for binding theencapsulating agent.
 3. The composition of claim 1, wherein theheterorotaxane has the structure:

where X is the first fluorophoric end group, Y is the centralfluorophoric group and Z is the second fluorophoric end group; N⁺ is aquarternary nitrogen cation; n is selected from 6, 7 and 8; R₁, R₂, R₃and R₄ are selected independently from the group consisting of H, alkylgroups, alkenyl groups, alkynyl groups, aryl groups, OH, NH₂, SH, F, Cl,Br, I, PR′₂, CHO, COOR′, COOM, CH₂OR′, CH₂OM, OR′, NHCOR′, CONHR′,CONHM, CONR′₂, N₃, NO₂, B(OR′)₂, B(OM)₂, CN, NR′³⁺, PR′³⁺, POR′₂, andOM, where R′ is selected independently from the group consisting of H,alkyl groups, alkenyl groups, alkynyl groups, and aryl groups and M isselected independently from the group consisting of Li, Na, K, Rb, andCs; and C⁻ is an organic or inorganic negatively charged ion.
 4. Thecomposition of claim 2, wherein the heterorotaxane has the structure:

where X is the first fluorophoric end group, Y is the centralfluorophoric group and Z is the second fluorophoric end group; N⁺ is aquarternary nitrogen cation; n is selected from 6, 7 and 8; R₁, R₂, R₃and R₄ are selected independently from the group consisting of H, alkylgroups, alkenyl groups, alkynyl groups, aryl groups, OH, NH₂, SH, F, Cl,Br, I, PR′₂, CHO, COOR′, COOM, CH₂OR′, CH₂OM, OR′, NHCOR′, CONHR′,CONHM, CONR′₂, N₃, NO₂, B(OR′)₂, B(OM)₂, CN, NR′³⁺, PR′³⁺, POR′₂, andOM, where R′ is selected independently from the group consisting of H,alkyl groups, alkenyl groups, alkynyl groups, and aryl groups and M isselected independently from the group consisting of Li, Na, K, Rb, andCs; and C⁻ is an organic or inorganic negatively charged ion.
 5. Thecomposition of claim 4, wherein where X, Y and Z are selected from thegroup consisting of pyrene, 2,9-diethyl-2,9-diazaperopyrenium dication,anthracene, coumarin, acridine, 9-aminoacridine, fluorescein,naphthofluorescein, resofurin, rhodamine B, rhodamine 6G, perylenediimide, naphthalene diimide, propidium, boron difluoridedipyrromethene, phthalocyanine, cyanine, porphyrin, and theirderivatives; N⁺ is selected from the group consisting ammonium, methylammonium, dimethyl ammonium and pyridinium cations; and C⁻ is selectedfrom the group consisting of F⁻, Cl⁻, Br⁻, I⁻, PF₆ ⁻, BF₄ ⁻, CF₃COO⁻,CH₃COO⁻, SO₄ ²⁻, SO₃ ²⁻, NO₃ ⁻, NO₂ ⁻, CO₃ ²⁻, HCO₃ ⁻, ClO₄ ⁻, PO₄ ³⁻,HPO₄ ²⁻, H₂PO₄ ⁻, CN⁻, and SCN⁻.
 6. The composition of claim 4, whereinX and Z are 1-pyrenylmethyl and Y is a 2,9-diazaperopyrenium dication.7. The composition of claim 1, wherein the encapsulating agent comprisesa γ-cyclodextrin.
 8. The composition of claim 2, wherein theencapsulating agent comprises a γ-cyclodextrin.
 9. The composition ofclaim 8, wherein the competitive binding agent comprises2-adamantylamine hydrochloride.
 10. A printhead comprising a pluralityof different ink channels, the different ink channels containingfluorescent ink compositions that comprise: (a) water; (b) aheterorotaxane comprising: (i) a substantially linear moleculecomprising a central fluorophoric group, a first fluorophoric end groupon one end of the substantially linear molecule, and a secondfluorophoric end group on the opposite end of the substantially linearmolecule; (ii) a first macrocyclic ring encircling the centralfluorophoric group; (iii) a second macrocyclic ring encircling a portionof the substantially linear molecule between the first fluorophoric endgroup and the central fluorophoric group; and (iv) a third macrocyclicring encircling a portion of the substantially linear molecule betweenthe second fluorophoric end group and the central fluorophoric group;(c) an encapsulating agent comprising a macrocyclic ring that is capableof encapsulating one or both of the first and second fluorophoric endgroups; and (d) optionally, a competitive binding agent that competeswith one or both of the first and second fluorophoric end groups forbinding the encapsulating agent.
 11. The printhead of claim 10, whereinthe fluorescent ink compositions in the different ink channels havedifferent concentrations of heterorotaxane, encapsulating agent and, ifpresent, competitive binding agent, such that the fluorescent inkcompositions in the different ink channels have different fluorescenceemission spectra.
 12. The printhead of claim 10, wherein the fluorescentink compositions in the different ink channels contain differentcompetitive binding agents, such that the fluorescent ink compositionsin the different ink channels have different fluorescence emissionspectra.
 13. A method of printing an image on a substrate, the methodcomprising applying one or more fluorescent ink compositions onto asurface of the substrate and allowing the one or more appliedfluorescent ink composition to dry, wherein the one or more fluorescentink compositions comprise: (a) water; (b) a heterorotaxane comprising:(i) a substantially linear molecule comprising a central fluorophoricgroup, a first fluorophoric end group on one end of the substantiallylinear molecule, and a second fluorophoric end group on the opposite endof the substantially linear molecule; (ii) a first macrocyclic ringencircling the central fluorophoric group; (iii) a second macrocyclicring encircling a portion of the substantially linear molecule betweenthe first fluorophoric end group and the central fluorophoric group; and(iv) a third macrocyclic ring encircling a portion of the substantiallylinear molecule between the second fluorophoric end group and thecentral fluorophoric group; (c) an encapsulating agent comprising amacrocyclic ring that is capable of encapsulating one or both of thefirst and second fluorophoric end groups; and (d) optionally, acompetitive binding agent that competes with one or both of the firstand second fluorophoric end groups for binding the encapsulating agent.14. The method of claim 13 comprising applying a plurality of thefluorescent ink compositions onto the surface of the substrate andallowing the plurality of applied fluorescent ink compositions to dry,wherein different fluorescent ink compositions within the plurality ofthe fluorescent ink compositions have different concentrations ofheterorotaxane, encapsulating agent and, if present, competitive bindingagent, such that the image printed on the substrate is a polychromicimage.
 15. The method of claim 13 comprising applying a plurality of thefluorescent ink compositions onto the surface of the substrate andallowing the plurality of applied fluorescent ink compositions to dry,wherein different fluorescent ink compositions within the plurality ofthe fluorescent ink compositions contain different competitive bindingagents, such that the image printed on the substrate is a polychromicimage.
 16. A printed substrate comprising: a substrate; and one or morefluorescent inks on the surface of the substrate, the fluorescent inkscomprising: (a) a heterorotaxane comprising: (i) a substantially linearmolecule comprising a central fluorophoric group, a first fluorophoricend group on one end of the substantially linear molecule, and a secondfluorophoric end group on the opposite end of the substantially linearmolecule; (ii) a first macrocyclic ring encircling the centralfluorophoric group; (iii) a second macrocyclic ring encircling a portionof the substantially linear molecule between the first fluorophoric endgroup and the central fluorophoric group; and (iv) a third macrocyclicring encircling a portion of the substantially linear molecule betweenthe second fluorophoric end group and the central fluorophoric group;(b) an encapsulating agent comprising a macrocyclic ring that is capableof encapsulating one or both of the first and second fluorophoric endgroups; and (c) optionally, a competitive binding agent that competeswith one or both of the first and second fluorophoric end groups forbinding the encapsulating agent.
 17. The printed substrate of claim 16comprising a plurality of the fluorescent inks on the surface of thesubstrate, wherein different fluorescent inks within the plurality ofthe fluorescent inks have different concentrations of heterorotaxane,encapsulating agent and, if present, competitive binding agent, suchthat the different fluorescent inks are different colors when viewedunder ultraviolet light.
 18. The printed substrate of claim 16comprising a plurality of the fluorescent inks on the surface of thesubstrate, wherein different fluorescent inks within the plurality ofthe fluorescent inks contain different competitive binding agents, suchthat the different fluorescent inks are different colors when viewedunder ultraviolet light.
 19. A method of authenticating a printedsubstrate, the printed substrate comprising: a substrate; and aplurality of fluorescent inks forming a polychromic image on the surfaceof the substrate, the fluorescent inks comprising: (a) a heterorotaxanecomprising: (i) a substantially linear molecule comprising a centralfluorophoric group, a first fluorophoric end group on one end of thesubstantially linear molecule, and a second fluorophoric end group onthe opposite end of the substantially linear molecule; (ii) a firstmacrocyclic ring encircling the central fluorophoric group; (iii) asecond macrocyclic ring encircling a portion of the substantially linearmolecule between the first fluorophoric end group and the centralfluorophoric group; and (iv) a third macrocyclic ring encircling aportion of the substantially linear molecule between the secondfluorophoric end group and the central fluorophoric group; (b) anencapsulating agent comprising a macrocyclic ring that is capable ofencapsulating one or both of the first and second fluorophoric endgroups; and (c) optionally, a competitive binding agent that competeswith one or both of the first and second fluorophoric end groups forbinding the encapsulating agent; the method comprising: applying anauthentication reagent over the polychromic image, wherein theauthentication reagent induces a change in the fluorescence emissionspectrum of the polychromic image; and comparing the change in thefluorescence emission spectrum of the polychromic image against a knownfluorescence emission spectrum change for an authentic printedsubstrate.
 20. The method of claim 19, wherein the authenticationreagent comprises a non-fluorescent encapsulating agent, anon-fluorescent competitive binding agent, or a combination thereof. 21.The method of claim 19, wherein the authentication reagent comprises afluorescent competitive binding agent.
 22. The method of claim 19,wherein the authentication reagent comprises a salt.
 23. The method ofclaim 19, wherein the authentication reagent is water.